Dyestuffs from phthalimide derivatives



Patented Jan. 9, 1951 JSTA'TES PM ENT oF-FicE "DYESTUFFS FBQM-IPHTHALMIDE DERIVATIVES William 10wen- Jones; Blackley, Manchester, Eng- ,Jand, assignor t-l3mperial= Chemical industries Limited, ,a corporation of" Great Britain No Drawing. Application August ,26,.1 9 4;'7, ,Serial No. 770.753. In-Great BritajngSenternber'fZ.

ness and good heat stability; and are particularly --valuab le as colouring matters.

Acc ording;to my invention' therefore' I 7 provide a-process forthemanufacture of new colouring matters which comprises condensing iminophthalimidine, thiophthalimide or iminothio- :;-.phthalimidine. or... a v nuclear substituted derivatiye. o any. Ofthese,substancesrwithfan aromatic ,primaryamine .or.a:hydrazine which contains. in

;additi0n-to;the amino; or hydrazino group either a -second;am ino-or hyd-razino .-group-,- or a substituted amino; or--hydrazino= group, -ora pendant-or ta .acondensed ringattached -to the aromatic nucleus.

As suitable nuclear substituted derivatives of iminophthalimidine, igninothiophthalimidine and thiophthalimide, there may be mentioned their vmethoxy, .chloro and :nitro derivativespand as ssuitable amines and" hydrazines "there-may be used :for example mandp-phenylenediamine, -z'-dehydrothio -p''toluidine," '2 i-aminobenzthiazole,

- aminoazobenzenegA1e. diaminoazobenzene,

i414 -,diaminostilbene;.benzidine, o-tolidine,- o-dianisidine, r3 :BZ-dichlorobenzidine, chloro-a- -naphthyIaminerZ aminoanthracene, 2-amino- .aminocarbazolecopper tetra aminophthaloi cyanine;2 4-dinitrophenylhydrazine andphenylhydrazine -sulphonic acid.

"5"Whemiininophthalimidine ora nuclear substi- -tuted derivative thereofis used in the condensation with an amine or a hydrazine, ammonia is split off during the condensation and when thicphthalimide or a nuclear substituted derivative thereof is used, hydrogen sulphide is--split ofi, the product in both casesbeing an arylimino "derivative or a mono hydrazone ciphthalimide. "When in'iinothiophthalimidine or, a nuclear .substituted .de vativ th reo ,is la t condensation,"'the imino group is,.. eli rninated. as

anthraquinone, 1.: 4 diaminoanthraquinone, 3-

ammonia-and an arylimino derivative or aimono- 3 hydrazone of 'thiophthalimide is formed.

When the amino or hydrazine-used contained two or more primary amino or hydrazinoi groups,

, it may condense withone-molecular proportion .efgthe iphthalimide. derivative or with. two or .more: molecular proportions depending .on the conditions used forthereaction andonthe number,- of amino and hydrazino groupsin the amine .1 .01: hydrazine. It isjnot usuallywpracticableuho evertin such cases -taisolate inapure state, the rreaction.product-of the. amine or hydrazine with soneimolecular -rproportioniof. .,the...phthalimide deeriva-tive. 1

e e Gt Q inl y. be b ou t abou -th simp y heating the reagents together or by heating the reagents togetherzinthelpresenoe of a suitable esolv nttornilucnt. .suitablas ventsare. fo xample v alcohohand. acetic .acid, ,the latter being particularly useful when ammonia is split off in' -the condensation.

Instead'of using the reagents mentioned, as t startin ma rials; other; substances ieldin the said reagents. under the conditions, of the interaction-may be-used ,For exampleinstead of -iminophthalimidine; o-cyanobenzamide may be .used. I

The eolouringematters obtained bythe process of this inventiommay {foreXample the. used. for

n3 colour=ing paperand also cell-vuloseacetate artiiicial. -silki-and nylon teX-tile materials, and for .,piementing polymeric materials-such-as forexa'rnple;polyvinyl chloride.

water soluble proclucts containing .sulph-onic The invention is illustrated but notlimitedby the following examples in which the parts are by weight.

tEmample. 1

1V rt -o r mi ephihel idine and 1.8, pa t ,cflsiehydroih cluidin a add iw f oiacetic acid andthen ixture is thenboiled for two minutes. llhe reaction; product separates from solution and forms a thick yellow paste which is then boiledswithtwater and filtered and finally jboi1ed.with ethanol, filtered and dried. 'lfhe yellow colouring matter so obtainedmay be rystal s iiii mi y en when; it o m bright ,y llcwneedles 7 C.

Instead of the 1.8 parts 0f dehy eptoluidine there may be employed 1.48 parts of p-aminoazobenzene. -The ;-product in this case when crysta lise liQ v.., I 1, 9133 o a M needleami132215.0-"

3 Example 2 1.6 parts of o-dianisidine hydrochloride, 1.5 parts of iminophthalimidine, 0.85 parts of fused sodium acetate and 3 parts of acetic acid are heated together at 100 C. for 1 hour. 50 parts of water are then added, the mixture is boiled for minutes and then filtered. The residue is washed with water and dried. The yellow coloured product so obtained melts at above 260 C.

Example 3 1.84 parts of benzidine, 2.15 parts of dichloro- 3-iminophthalimidine obtained as described below, and parts of 80% aqueous acetic acid are heated together for 1 hour on the steam bath. The orange-yellow reaction product which separates during the heating is filtered, washed with water and dried. It melts above 300 C.

The dichloro-3-iminophthalimidine (M. P. 295 C.) employed in this reaction may be obtained by heating 3:4-dichlorophthalimide with urea at ISO-170 C. in the presence of ammonium vanadate.

Example 4 1.9 parts of nitro-iminophthalimidine (obtained by heating 4-nitro-phthalimide with urea at ISO-170 C. in the presence of ammonium vanadate) are mixed with 1.9 parts p-sulphophenylhydrazine and a small crystal of iodine, and the mixture is heated with parts of ethanol on the steam bath for 1 hours. On cooling, 3.2 parts of an orange-brown solid are obtained. This material is readily soluble in water and dyes wool in a bright orange shade.

Example 5 1.6 parts of o-dianisidine hydrochloride, 1.75 parts of methoxy 3 iminophthalimidine (obtained as described below), 0.85 part of fused sodium acetate and 5 parts of acetic acid are heated together at 100 C. for 1 hour. 50 parts wa ter are then added, the mixture boiled and then filtered, washed with water and dried. The bright yellow product so obtained melts at above 260 C.

The methoxy-3-iminophthalimidine employed in this example is obtained from 4-methoxyphthalimide, which is converted by the action of concentrated aqueous ammonia solution to 4- methoxyphthalamide (M. P. 189 C. with ammonia evolution) which is then dehydrated with acetic anhydride to give 4- (or 5-) methoxy-2- cyanobenzamide (M. P. 164-6 0.), which is heated above its melting point to isomerise it to the 6- (or 5-)methoxy-iminophthalimidine (M. P. 233-5 C.).

Example 6 Instead of 1.1 parts of imino-phthalimidine used in Example 1 there can be used 1.44 parts of nitro-iminophthalimidine (obtained by heating 3-nitro-phthalimide with urea at 160-170 C. in the presence of ammonium vanadate). The product is an orange coloured solid.

Example 7 9.2 parts of benzidine and 14.6 parts of ocyanobenzamide are intimately mixed and heated with stirring at 200 C. for 30 minutes. The product is crystallised from o-dichlorobenzene in yellow crystals melting above 300 0.

Example 8 A mixture of 1.6 parts of o-dianisidine hydrochloride, 1.65 parts of imino-thiophthalimidine,

0.85 part of fused sodium acetate and 10 parts of acetic acid is heated on the steam bath for one hour. The product is filtered hot, washed with 10 parts of acetic acid, then with 200 parts of water and finally with parts of ethanol. The red colouring matter so obtained may be crystallised from o-dichlorobenzene, and it has melting point 289 C.

The imino-thiophthalimidine used as starting material may be prepared by passing hydrogen sulphide into a cold suspension of phthalonitrile in aqueous alcoholic sodium hydrogen sulphide. The resulting green solution is filtered and the imino-thiophthalimidine is precipitated from the filtrate as an orange solid on adding hydrochloric acid to reduce the alkalinity.

Example 9 7.5 parts of imino-phthal midine and 2.75 parts of p-phenylenediamine are mixed together and charged into a stirred mixture of 20 parts of acetic acid and 100 of ethanol at 70 C. A deep orange solution results from which a yellow solid then separates. After 1 hour the mixture is filtered and washed with ethanol. The bright-yellow compound so obtained melts above 300 C.

Example 10 3 parts of 2-aminobenzthiazole and 3 parts of imino-phthalimidine are ground together and melted at 210-220 C. with stirring. Ammonia is freely evolved and the mixture solidifies. After about 3 minutes the product is boiled with 50 parts of acetic ac dand allowed to cool. The bright yellow needles (M. P. 222 C.) which separate are filtered off, washed with water and dried.

Example 11 4 parts of imino-phthalimidine, 4 parts of o-dianisidine hydrochloride and 2.2 parts of fused sodium acetate are intimately mixed and heated at 200-220 C. for 1 hour. Ammon a gas is evolved during the reaction. The product is extracted with hot water and then with ethanol. The yellow coloured product obtained is identical with that described in Example 2.

Example 12 1 part of thiophthalimide, 0.8 part of phenyl hydrazine and 8 parts of acetic acid are heated together at the boil with stirring. Hydrogen sulphide is evolved and after two minutes there is a sudden separation of yellow solid. The mixture is diluted with water and filtered and the residue washed and dried. The product forms beautiful yellow needles when crystallised from 2-ethoxyethanol which melt at 227-229 C. and it may be regarded as the mono-phenylhydrazone of phthalimide. This new compound is soluble in dilute caustic soda from which it is precipitated unchanged on acidification. The dispersed pigment dyes acetate silk and nylon in lemon yellov shades.

Example 13 2 parts of imino-phthalimidine, 2 parts of phenyl hydrazine hydrochloride and 1.4 parts of fused potassium acetate are mixed and then heated with 40 parts of ethanol on the steam bathfor V hour. 3.2 parts of a sparingly soluble yellow product are obtained identical with the product of Example 12.

5 I claim: 1. New compounds having the general formula:

R1 fi B1 R NH HN R2 C/ i R wherein A is a radical from the group consisting of =0 and =S, R is a divalent aryl radical, R is a radical selected from the group consisting of H, C1,OCH3 and NO2 and R, is a radical selected from the group consisting of H and -C1.

2. New compounds of the general formula:

wherein R is a divalent aryl radical.

3. The yellow-colored compound having the formula:

i a H A 0/ OCHa C im i 4. The orange-yellow-colored compound having the formula:

35 Number 5. The yellow-colored compound having the formula:

0 o -i (L OHZO \NH HN/ 0 CH3 -c 0 CH3 0 cH@ o- M i 6. The red-colored compound havin the formula:

WILLIAM OWEN JONES.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Name Date Sandmeyer Apr. 10, 1900 OTHER REFERENCES Drew and Kelly: Jour. Chem. Soc. (London) (1941) pp. 625 to 641. r 

1. NEW COMPOUNDS HAVING THE GENERAL FORMULA: 